Hole Doping Research Articles

Electronic structure and magnetothermal property of two-dimensional ferromagnetic NbSe2 monolayer regulated by carrier concentration

Investigating high-performance and stable spintronics devices has been a research hotspot in recent years. In this paper, we employed first-principles methods and Monte Carlo (MC) simulations to explore the structure, electronic, and magnetic properties of monolayer NbSe2, as well as its behavior under carrier concentration modulation. The research on the electronic structure reveals that by introducing an appropriate amount of holes, the material can undergo a transition from metal to a half-metal state, achieving 100% high spin polarization. Investigation of magnetic crystalline anisotropy shows that the magnetic crystal anisotropy energy of 1210 μeV in out-of-plane is beneficial to maintain ferromagnetic order at high temperatures. In addition, doping with suitable carriers can effectively enhance or strengthen the ferromagnetic coupling in NbSe2 so that the magnetization easy axis is shifted. This reveals the potential application prospects of NbSe2 in electronically controlled spintronic devices. Analysis of the Fermi surface shows that both holes and electron doping increase the Fermi velocity of the material. The effect of hole doping is particularly significant, indicating its potential application in Fermi velocity engineering. Under the theoretical framework of the extended two-dimensional Ising model, based on MC simulation, the Curie temperature (TC) of NbSe2 is predicted to be 162 K. The effects of carrier concentration and the magnetic field on the magnetic and thermal properties of monolayer NbSe2 are simulated. The results show that appropriately increasing the hole doping concentration and magnetic field is conducive to obtaining ferromagnetic half-metallic materials with TC higher than room temperature, which provides theoretical support for experimental preparation.

Room temperature high thermoelectric performance of Bi-based full-Heusler compounds CsxRb[formula omitted]Bi with strong anharmonicity

Bismuth-based compounds have been identified as a class of promising candidates for the realization of high-performance thermoelectrics, derived from their exceptional electrical conductivity and intrinsic low lattice thermal conductivity κL. Here, we employed first-principles calculations, self-consistent phonon theory, and compressive sensing technique in conjunction with the Boltzmann transport equation to investigate the anharmonic thermoelectric properties of full-heusler bismuth compounds CsxRb3−xBi. As the Cs content increases, the κL of CsxRb3−xBi decreases due to impurity scattering effects, and then increases. Among them, at 300 K, Rb3Bi has the largest κL of 0.69 Wm−1K−1, while Cs2RbBi has the smallest κL of 0.45 Wm−1K−1, both of which are lower than the κL of traditional bismuth-based thermoelectric materials. The ultralow κL originates from the strong lattice anharmonicity. In addition, the coexistence of high dispersion and flat band edges leads to high thermoelectric power factor at optimal doping concentration. As a result, the largest thermoelectric figure of merit ZT values of 2.59 (4.19) at 300 (500) K were obtained for CsRb2Bi at optimal hole doping level. These findings suggest that CsxRb3−xBi compounds are superior for thermal management and thermoelectric applications.

Promoted Electronic Coupling of Acoustic Phonon Modes in Doped Semimetallic MoTe2.

As a prototype of the Weyl superconductor, layered molybdenum ditelluride (MoTe2) encompasses two semimetallic phases (1T' and Td) which differentiate from each other via a slight tilting of the out-of-plane lattice. Both phases are subjected to serious phase mixing, which complicates the analysis of its origin of superconductivity. Herein, we explore the electron-phonon coupling (EPC) of the monolayer semimetallic MoTe2, without phase ambiguity under this thickness limit. Apart from the hardening or softening of the phonon modes, the strength of the EPC can be strongly modulated by doping. Specifically, longitudinal and out-of-plane acoustic modes are significantly activated for electron doped MoTe2. This is ascribed to the presence of rich valley states and equispaced nesting bands, which are dynamically populated under charge doping. Through comparing the monolayer and bilayer MoTe2, the strength of EPC is found to be less likely to depend on thickness for neutral samples but clearly promoted for thinner samples with electron doping, while for hole doping, the strength alters more significantly with the thickness than doping. Our work explains the issue of the doping sensitivity of the superconductivity in semimetallic MoTe2 and establishes the critical role of activating acoustic phonons in such low-dimensional materials.

Influence of topology on the phase transition of a ferromagnetic metal

The topological ferromagnet CoS2 exhibits an anhysteretic, weakly first-order transition at the Curie temperature of 119.8 K with a tricritical point µ0Htcp at 0.034 T. Magnetic symmetry and the mixing of majority and minority spin eg bands at a subband crossing just above the Fermi level produce a topological component of the magnetization that leads to a negative M3 term in the Landau free energy. The position of the Fermi level relative to the subband crossing is critical for controlling the order of the transition. Hole doping in Co0.89Fe0.11S2 drains the minority-spin eg pocket and results in a normal second-order phase transition. Electron doping in Co0.94Ni0.06S2 raises the Fermi level toward the subband gap, producing a strongly first-order transition with 15 K hysteresis. Our results demonstrate a relation between topological electronic structure and thermal hysteresis at the Curie point, which may help in the search for magnetocaloric materials.

Hartree–Fock with Nambu spinors, and d-wave condensation in the 2D Hubbard model

The usual Hartree–Fock approximation to the Hubbard model is based on eigenstates of the electron number operator. But this formulation is not unique. A different (and inequivalent) version, formulated in terms of Nambu two-component spinors, is based on eigenstates of the difference between the numbers of spin up and spin down electrons, with electron density dependent on parameters U,t,t′ and chemical potential μ. The advantage of this formulation is that electron pairing condensates can be directly computed. We show that in the ground states away from half-filling, obtained in this “Nambu” Hartree–Fock approximation, a discrete rotation symmetry is spontaneously broken, and the condensates exhibit the expected d-wave form in momentum space. We also show that the Mott insulator electron configuration is obtained in this formulation at large U/t and half-filling, and roughly locate the boundary, in the hole doping−U/t plane, between a region of local antiferromagnetism and stripe/domain formation, and the region of d-wave condensation.

Charge Distribution across Capped and Uncapped Infinite-Layer Neodymium Nickelate Thin Films.

Charge ordering (CO) phenomena have been widely debated in strongly-correlated electron systems mainly regarding their role in high-temperature superconductivity. Here, the structural and charge distribution in NdNiO2 thin films prepared with and without capping layers, and characterized by the absence and presence of CO are elucidated. The microstructural and spectroscopic analysis is done by scanning transmission electron microscopy-electron energy loss spectroscopy (STEM-EELS) and hard X-ray photoemission spectroscopy (HAXPES). Capped samples show Ni1+ , with an out-of-plane (o-o-p) lattice parameter of around 3.30 Å indicating good stabilization of the infinite-layer structure. Bulk-sensitive HAXPES on Ni-2p shows weak satellite features indicating large charge-transfer energy. The uncapped samples evidence an increase of the o-o-p parameter up to 3.65 Å on the thin film top with a valence toward Ni2+ in this region. Here, 4D-STEM demonstrates (303)-oriented stripes which emerge from partially occupied apical oxygen. Those stripes form quasi-2D coherent domains viewed as rods in the reciprocal space with Δqz ≈ 0.24 reciprocal lattice units (r.l.u.) extension located at Q = ( ) and ( ) r.l.u. The stripes associated with oxygen re-intercalation concomitant with hole doping suggest a possible link to the previously reported CO in infinite-layer nickelate thin films.

Effects of Ni/Co doping on structural and electronic properties of 122 and 112 families of Eu based iron pnictides

Superconductivity in high-temperature superconductors such as cuprates or iron pnictides is typically achieved by hole or electron doping and it is of great interest to understand how doping affects their properties leading to superconductivity. To study it we conducted Fe and As K edge x-ray absorption spectroscopy measurements on several electron doped compounds from the 112 and 122 family of Eu-based iron pnictides. XANES and EXAFS results confirm that dopants are located at expected sites. For both families we found an electron charge redistribution between As and Fe occurring with doping. The changes it caused are stronger in the 112 family and they are bigger at As sites, which indicates that doped charges are predominantly localized on the dopant site. However, the results obtained do not provide clues why Ni doping in 122 family does not lead to occurrence of superconductivity.

Growth and Electronic Structure of Copper Oxide Monolayer Epitaxial Films.

Copper-based high-temperature superconductors share a common feature in their crystal structure, which is the presence of a CuO2 plane, where superconductivity takes place. Therefore, important questions arise as to whether superconductivity can exist in a single layer of the CuO2 plane and, if so, how such superconductivity in a single CuO2 plane differs from that in a bulk cuprate system. To answer these questions, studies of the superconductivity in cuprate monolayers are necessary. In this study, we constructed a heterostructure system with a La2-xSrxCuO4 (LSCO) monolayer containing a single CuO2 plane and measured the resulting electronic structures. Monolayer LSCO has metallic and bulk-like electronic structures. The hole doping ratio of the monolayer LSCO is found to depend on the underlying buffer layer due to the interface effect. Our work will provide a platform for research into ideal two-dimensional cuprate systems.

Realizing metallicity in Sr2IrO4 thin films by high-pressure oxygen annealing

Perovskite iridates are a promising material platform for hosting unconventional superconductivity. Transport measurements of Sr2IrO4 thin-film field-effect transistors are expected to provide irrefutable evidence for the existence of superconductivity. However, these experiments have revealed a remarkably robust insulating state over wide electron and hole doping ranges; this finding is in contrast to the case of the bulk material, in which metallicity appears upon moderate electron doping by substituting cations in place of Sr. The nature of this robust insulating state and whether any metallic state can be realized in the Sr2IrO4 thin film are two remaining challenges that preclude further progress in the search for superconductivity in this system. Here, we show that this insulating state is enhanced in Sr2IrO4 thin films by thermal annealing under vacuum conditions, while it can be destroyed upon annealing in an oxygen atmosphere within restricted ranges of oxygen pressure, annealing temperature and ion substitution levels. The resulting films exhibit metallic transport behavior near room temperature and a metal–insulator crossover at ~200 K. Our results point to the potentially important roles of the oxygen vacancies at different atomic sites in the formation of the robust insulating state and the new metallic state and to their interplay in the Sr2IrO4 thin film. This finding opens new possibilities in the search for unconventional superconductivity by further tailoring the as-found metallic state in properly oxygen-annealed Sr2IrO4 thin films.

Magnetic Second‐Order Topological Insulator: An Experimentally Feasible 2D CrSiTe3

Abstract2D second‐order topological insulators (SOTIs) have sparked significant interest, but currently, the proposed realistic 2D materials for SOTIs are limited to nonmagnetic systems. In this study, for the first time, a single layer of chalcogenide CrSiTe3—an experimentally realized transition metal trichalcogenide is proposed with a layer structure—as a 2D ferromagnetic (FM) SOTI. Based on first‐principles calculations, this study confirms that the CrSiTe3 monolayer exhibits a nontrivial gapped bulk state in the spin‐up channel and a trivial gapped bulk state in the spin‐down channel. Based on the higher‐order bulk–boundary correspondence, it demonstrates that the CrSiTe3 monolayer exhibits topologically protected corner states with a quantized fractional charge () in the spin‐up channel. Notably, unlike previous nonmagnetic examples, the topological corner states of the CrSiTe3 monolayer are spin‐polarized and pinned at the corners of the sample in real space. Furthermore, the CrSiTe3 monolayer retains SOTI features when the spin–orbit coupling (SOC) is considered, as evidenced by the corner charge and corner states distribution. Finally, by applying biaxial strain and hole doping, this study transforms the magnetic insulating bulk states into spin‐gapless semiconducting and half‐metallic bulk states, respectively. Importantly, the topological corner states persist in the spin‐up channel under these conditions.

Electronic phase transition, perpendicular magnetic anisotropy and high Curie temperature in Janus FeClF

How to enhance the spin polarization, the Curie temperature and the perpendicular magnetic anisotropy (PMA) is crucial for the applications of 2D magnets in spintronic devices. In this work, based on the experimental FeCl2 flakes and the predicted in-plane magnetic anisotropy (IMA) and lower Curie temperature of FeCl2 monolayer, we use first-principles and Monte Carlo simulation to explore the strain and carrier-doping effects on the electronic and magnetic properties of Janus FeClF monolayer. The structure is stable within −10% to 2% biaxial strain. Janus FeClF monolayer can experience transitions from a half-semiconductor to a spin gapless semiconductor (SGS) around the −6% compressive strain, and from the IMA to the PMA at the −7% compressive strain. The super-exchange Fe–F/Cl–Fe interaction induces the ferromagnetic coupling, and the Curie temperature can be considerably enhanced from 56 K to 281 K at the −10% compressive strain. The half-metallicity can be achieved whether under electron doping or hole doping. The Fe-d orbitals and the spin–orbit coupling interaction between occupied and unoccupied intraorbital states are responsible for the electronic phase transition and the magnetic anisotropy, respectively. Remarkably, the compressive −10% strain and the 0.02 e doping collectively increase the Curie temperature to near room temperature (286 K). The high spin polarization (exhibiting SGS and half-metal), the PMA and the near-room-temperature ferromagnetism induced by strain and doping make Janus FeClF a promising candidate for 2D spintronic applications, which will stimulate experimental and theoretical broad studies on this class of Janus monolayers FeXY (X,Y = F, Cl, Br, and X ≠ Y).

Incommensurate Magnetic Order in Hole‐Doped Infinite‐Layer Nickelate Superconductors due to Competing Magnetic Interactions

AbstractThe discovery of superconductivity in hole‐doped infinite‐layer nickelates has fueled intense research to identify the critical factor responsible for high‐Tc superconductivity. Magnetism and superconductivity are closely entangled, and elucidating the magnetic interactions in hole‐doped nickelates is critical for understanding the pairing mechanism. Here, these calculations based on the generalized Bloch theorem (GBT) and magnetic force theorem (MFT) consistently reveal that hole doping stabilizes an incommensurate (IC) spin state and increases the IC wave vector continuously, in a way strikingly similar to hole‐doped cuprates. Going further, a nonlinear Heisenberg model including first‐neighbor and third‐neighbor in‐plane magnetic interactions is developed. The analytical solutions successfully reproduce GBT and MFT results and reveal that the competition between the two magnetic interactions is the decisive factor for the IC magnetic transition. Eventually, by analyzing the doping‐controlled spin splitting of band and orbital‐contributed exchange interactions, direct links between hole doping, magnetization, exchange constants, and magnetic order are established. This discovery of the IC spin state, new understanding of its electronic origin, and establishment of direct connection with the paring electrons radically change the current understanding of the magnetic properties in hole‐doped NdNiO2 and open new perspectives for the superconducting mechanism in nickelates superconductors.

Dynamical spin structure factors of GeCH3 monolayer due to spin-orbit coupling, strain, and external magnetic field

In this study, we introduced the Kane-Mele model in the presence of an external magnetic field and used a tight-binding approach to examine the dynamical spin susceptibility of the GeCH3 monolayer. We employed Green's function technique to determine the dynamical spin susceptibility behavior of the GeCH3 monolayer in the presence of an external magnetic field, strain, spin-orbit coupling (SOC), electron, and hole doping at room temperature. Our results show that the transverse excitation modes tend to move to lower (higher) frequencies with tensile (compressive) biaxial strain.In addition, the frequency position of the sharp peak in the transversedynamical spin susceptibility is not affected by changes in the external magnetic field, electron doping, or SOC. Also, the influences of the wave vector and doping on the frequency dependence of the transversedynamical spin susceptibility are studied in detail. These results offered here exhibit that the GeCH3 monolayer is appropriate for use in detectors.

Janus monolayer ScXY (X≠Y = Cl, Br and I) for piezoelectric and valleytronic application: a first-principle prediction

Coexistence of ferromagnetism, piezoelectricity and valley in two-dimensional (2D) materials is crucial to advance multifunctional electronic technologies. Here, Janus ScXY (X≠Y = Cl, Br and I) monolayers are predicted to be piezoelectric ferromagnetic semiconductors with dynamical, mechanical and thermal stabilities. They all show an in-plane easy axis of magnetization by calculating magnetic anisotropy energy (MAE) including magnetocrystalline anisotropy energy and magnetic shape anisotropy energy. The MAE results show that they intrinsically have no spontaneous valley polarization. The predicted piezoelectric strain coefficients d 11 and d 31 (absolute values) are higher than ones of most 2D materials. Moreover, the d 31 (absolute value) of ScClI reaches up to 1.14 pm V−1, which is highly desirable for ultrathin piezoelectric device application. To obtain spontaneous valley polarization, charge doping are explored to tune the direction of magnetization of ScXY. By appropriate hole doping, their easy magnetization axis can change from in-plane to out-of-plane, resulting in spontaneous valley polarization. Taking ScBrI with 0.20 holes per f.u. as an example, under the action of an in-plane electric field, the hole carriers of K valley turn towards one edge of the sample, which will produce anomalous valley Hall effect, and the hole carriers of Γ valley move in a straight line. These findings could pave the way for designing piezoelectric and valleytronic devices.

Ultralow lattice thermal conductivities and excellent thermoelectric properties of hypervalent triiodides XI3 (X = Rb, Cs) discovered by machine learning method.

Thermal conductivity and power factor are key factors in evaluating heat transfer performance and designing thermoelectric conversion devices. To search for materials with ultralow thermal conductivity and a high power factor, we proposed a set of universal statistical interaction descriptors (SIDs) and developed accurate machine learning models for the prediction of thermoelectric properties. For lattice thermal conductivity prediction, the SID-based model achieved the state-of-the-art results with an average absolute error of 1.76W m-1 K-1. The well-performing models predicted that hypervalent triiodides XI3 (X = Rb, Cs) have ultralow thermal conductivities and high power factors. Combining first-principles calculations, the self-consistent phonon theory, and the Boltzmann transport equation, we obtained the anharmonic lattice thermal conductivities of 0.10 and 0.13W m-1 K-1 for CsI3 and RbI3 in the c-axis direction at 300K, respectively. Further studies show that the ultralow thermal conductivity of XI3 arises from the competition of vibrations between alkali metal atoms and halogen atoms. In addition, at 700K, the thermoelectric figure of merit ZT values of CsI3 and RbI3 are 4.10 and 1.52, respectively, at the optimal hole doping level, which indicates hypervalent triiodides are potential high performance thermoelectric materials.

Spectroscopic studies of the superconducting gap in the 12442 family of iron-based compounds (Review article)

The iron-based compounds of the so-called 12442 family are very peculiar in various respects. They originate from the intergrowth of 122 and 1111 building blocks, display a large in-plane vs out-of-plane anisotropy, possess double layers of FeAs separated by insulating layers, and are generally very similar to double-layer cuprates. Moreover, they are stoichiometric superconductors because of an intrinsic hole doping. Establishing their superconducting properties, and in particular the symmetry of the order parameter, is thus particularly relevant in order to understand to what extent these compounds can be considered as the iron-based counterpart of cuprates. In this work, we review the results of various techniques from the current literature and compare them with ours, obtained in Rb–12442 by combining point-contact Andreev reflection spectroscopy and coplanar waveguide resonator measurements of the superfluid density. It turns out that the compound possesses at least two gaps, one of which is certainly nodal. The compatibility of this result with the theoretically allowed gap structures, as well as with the other results in literature, is discussed in detail.

Transient dynamics and quantum phase diagram for the square lattice Rashba-Hubbard model at arbitrary hole doping

Transient dynamics and quantum phase diagram for the square lattice Rashba-Hubbard model at arbitrary hole doping

Ambipolar Doping of Monolayer FeSe by Interface Engineering

We report on ambipolar modulation doping of monolayer FeSe epitaxial films grown by molecular beam epitaxy and in situ spectroscopic measurements via a cryogenic scanning tunneling microscopy. It is found that hole doping kills superconductivity in monolayer FeSe films on metallic Ir(001) substrates, whereas electron doping from polycrystalline IrO2/SrTiO3 substrate enhances significantly the superconductivity with an energy gap of 10.3 meV. By exploring substrate-dependent superconductivity, we elucidate the essential impact of substrate work functions on the superconductivity of monolayer FeSe films. Our results therefore offer a valuable reference guide for further enhancement of the transition temperature T c in FeSe-based superconductors by interface engineering.

Magnetocaloric effect in the Ising model with RKKY interaction on the Shastry–Sutherland lattice

The classical Monte Carlo method is used to examine effects of electron and hole doping on the magnetocaloric effect in the generalized 2D Ising model with the long-range RKKY interaction on the Shastry–Sutherland lattice. The electron and hole doping in this model is controlled by deviations of the Fermi wave vector kF from the initial value kF=2π/1.24 which models the most realistically situation in the undoped metallic Shastry–Sutherland rare-earth tetraboride TmB4. For the undoped case we have found a heating hill (the entropy change ΔS>0) occurring in the vicinity of metamagnetic transitions and a cooling depression in the paramagnetic phase which is in a very good qualitative agreement with experimental measurements in TmB4. In the case of small electron doping (kF=2π/1.26), a significant decrease of the maximum of −ΔS is observed, while in the strongly hole (electron) doped case kF=2π/1.17 (kF=2π/1.43) the maximum of −ΔS is considerably enhanced against the undoped system, which points to the fact that some of doped systems could have better cooling properties than the undoped one. This is confirmed independently by calculations of relative cooling power for a wide range of parameter kF, where we have found two intervals kF∈〈2π/1.15,2π/1.21〉 and kF∈〈2π/1.39,2π/1.5〉 with much larger relative cooling power in comparison to the undoped case.

Hole and Electron Doping Outcomes in Bi2YO4Cl.

Recognizing the deficiency in the hole and electron doping outcomes in layered bismuth-based oxyhalides intergrowths, the current study was addressed to the doping of Ca2+ and Zr4+ for Y3+ in Bi2YO4Cl. The samples were rapidly synthesized by a sol-gel auto combustion method and characterized extensively. Up to 30 mol % Y could be substituted with Ca in tetragonal symmetry and without the appearance of any additional phase. The unit cell parameters varied nonlinearly with the elongation of the Y-O bond. The Raman spectra supported the local site distortion. The calcium-substituted samples displayed selected area electron diffraction characteristics similar to those of Bi2YO4Cl. A blueshift of the absorption edge was noticed with increasing calcium content yielding optical band gap values in the 2.40-2.57 eV range. The creation of 10% Bi5+ in Bi2Y0.70Ca0.30O4Cl was established with the help of XPS measurements and redox titrations. The higher reactivity of Bi5+ in an aqueous solution has been demonstrated for the oxidation of As(III) to As(V). Electron doping through Zr4+ incorporation was possible up to 30 mol % in Bi2YO4Cl. The Y-O bonds are contracted, and the Bi-O bonds are elongated with increasing Zr4+ content. Zr4+'s incorporation induced a local distortion. The color of the sample changed from bright yellow to deep yellow with Zr inclusion, resulting in a progressive decrease in optical band gap values. The introduction of electrons caused the reduction of 13.6% of Bi(III) to Bi(0). These results have established the vulnerability of Bi2O2 chains to charge carriers in Bi2YO4Cl. Density functional theory (DFT) calculations were implemented to understand the electronic and optical properties of the pristine and doped compounds. From the band structure calculations, the chosen compounds were found to be indirect band gap semiconductors. The results of the DFT calculations were in good agreement with the experiment; however, for the doped cases, virtual crystal approximation has been used considering uniform doping at the Y-site.